Effects of size and composition of bitumen drops on intra-oil diffusion and dissolution of hydrocarbon solvents in froth treatment tailings ponds.

The rate of mass transfer of lower molecular weight hydrocarbons (naphtha) from bitumen drops in mature fine tailings of oil sand tailings ponds (OSTPs) may control their bioavailability and the associated rate of GHG production. Experiments were conducted using bitumen drops spiked with o-xylene and 1-methylnaphthalene to determine the mass transfer rate of these naphtha components from bitumen drops. The results were compared to simulations using a multi-component numerical model that accounted for transport in the drop and across the oil-water interface. The results demonstrate rate-limited mass transfer, with aqueous concentrations after 60 days of dissolution that were different than those in equilibrium with the initial drop composition (less for o-xylene and greater for 1-methylnaphthalene). The simulations suggest that mole fractions were unchanged at the center of the drop, resulting in concentration gradients out to the oil-water interface. Numerical simulations conducted using different drop sizes and bitumen viscosities also suggest the potential for persistent naphtha dissolution, where the time required to deplete 80% of the o-xylene and 1-methylnaphthalene mass from an oil drop was estimated to be on the order of months to years for mm-sized drops, and years to decades for cm-sized drops assuming instantaneous biodegradation in the aqueous phase surrounding the bitumen.

Effects of dissolved organic phase composition and salinity on the engineered sulfate application in a flow-through system.

Engineered sulfate application has been proposed as an effective remedy to enhance the rate-limited biodegradation of petroleum-hydrocarbon-contaminated subsurface environments, but the effects of dissolved organic phase composition and salinity on the efficiency of this method are unknown. A series of flow-through experiments were conducted for 150 days and dissolved benzene, toluene, naphthalene, and 1-methylnaphthalene were injected under sulfate-reducing and three different salinity conditions for 80 pore volumes. Then, polycyclic aromatic hydrocarbons (PAHs) were omitted from the influent solution and just dissolved benzene and toluene were injected to investigate the influence of dissolved phase composition on treatment efficiency. A stronger sorption capacity for PAHs was observed and the retardation of the injected organic compounds followed the order of benzene < toluene < naphthalene < 1-methylnaphthalene. Mass balance analyses indicated that 50 and 15% of toluene and 1-methlynaphtalene were degraded, respectively. Around 5% of the injected naphthalene degraded after injecting > 60 PVs influent solution, and benzene slightly degraded following the removal of PAH compounds. The results showed substrate interactions and composition can result in rate-limited and insufficient biodegradation. Similar reducing conditions and organic utilization were observed for different salinity conditions in the presence of the multi-component dissolved organic phase. This was attributed to the dominant microbial community involved in toluene degradation that exerted catabolic repression on the simultaneous utilization of other organic compounds and were not susceptible to changes in salinity.

Intra-NAPL diffusion and dissolution of a MGP NAPL exposed to persulfate in a flow-through system.

Intra-NAPL diffusion is a critical process that can influence NAPL/water mass transfer. A series of physical model experiments was performed to investigate the role of intra-NAPL diffusion on the transient dissolution of a complex multicomponent NAPL subjected to persulfate treatment. To support these observations, a diffusion-based model was developed and calibrated using the experimental data. The experimental results indicated that while persulfate was able to completely degrade dissolved phase components, mass loss after ∼410 pore volumes of persulfate flushing was less than the no-treatment system. Intra-NAPL diffusion limitations were not observed in the physical model experiments. A comparison of experimental and simulated results indicated that processes related to persulfate/NAPL interactions restricted mass transfer, and yielded multicomponent mass transfer rate coefficients that were ∼30% of those estimated from an equivalent water-flushing experiment. Simulation results showed that a combination of NAPL composition and geometry, and interphase mass transfer rate can yield intra-NAPL diffusion limitations. Remedial technologies that rely on the aggressive flushing of reagents into NAPL zones may give rise to intra-NAPL diffusion limitations, which will directly affect treatment efficiency.

Realistic expectations for the treatment of FMGP residuals by chemical oxidants.

Methods to remediate soil and groundwater contamination at former manufactured gas plant (FMGP) sites are scarce. The objective of this study was to investigate the ability of two chemical oxidants (persulfate and permanganate) to degrade FMGP residuals in a dynamic system representative of in situ conditions. A series of physical model trials supported by aqueous and slurry batch experiments using impacted sediments collected from a FMGP site were conducted. To explore treatment expectations a screening model constrained by the experimental data was employed. The results from the aqueous experiments showed that dissolved components (except for benzene) were readily degraded by persulfate or permanganate. In the well-mixed slurry systems, when contact with the oxidant was achieved, 95%, 45% and 30% of the initial mass quantified was degraded by permanganate, unactivated persulfate, and alkaline activated persulfate, respectively. In stark contrast, the total mass removed in the physical model trials was negligible for both permanganate and persulfate irrespective of the bleb or lense architecture used. Hence the net benefit of flushing 6 pore volumes of permanganate or persulfate at a concentration of 30 g/L under the physical model operating conditions was minimal. To achieve a substantial degradation of mass within the treatment system (>40%), results from the screening model indicated that the hydraulic resident time would need to be >10 days and the average lumped mass transfer coefficient increased by two orders-of-magnitude. Results from long-term (5 years) simulations showed that the dissolved concentrations of organic compounds are reduced temporarily as a result of the presence of permanganate but then rebound to a profile that is essentially coincident with a no-treatment scenario following exposure to permanganate. Neither a lower velocity nor higher permanganate dosing affected the long-term behavior of the dissolved phase concentrations; however, increasing the mass transfer rate coefficient had an impact. The findings from this investigation indicate that the efficiency of permanganate or persulfate to treat for FMGP residuals is mass transfer limited.

The role of intra-NAPL diffusion on mass transfer from MGP residuals.

An experimental and computational study was performed to investigate the role of multi-component intra-NAPL diffusion on NAPL-water mass transfer. Molecular weight and the NAPL component concentrations were determined to be the most important parameters affecting intra-NAPL diffusion coefficients. Four NAPLs with different viscosities but the same quantified mass were simulated. For a spherical NAPL body, a combination of NAPL properties and interphase mass transfer rate can result in internal diffusion limitations. When the main intra-NAPL diffusion coefficients are in the range of self-diffusion coefficients (10-5 to 10-6 cm2/s), dissolution is not limited by internal diffusion except for high mass transfer rate coefficients (>180 cm/day). For a complex and relatively high viscous NAPL (>50 g/(cm s)), smaller intra-NAPL diffusion coefficients (<10-8) are expected and even low mass transfer rate coefficients (~6 cm/day) can result in diffusion-limited dissolution.